%0 Journal Article %T A new photoionization-induced substitution reaction chemical ionization time-of-flight mass spectrometry for highly sensitive detection of trace exhaled ethylene. %A Zhang B %A Hua L %A Fan Z %A Wen Y %A Zhang L %A Xie Y %A Gao Y %A Jiang J %A Li H %J Anal Chim Acta %V 1317 %N 0 %D 2024 Aug 15 %M 39030010 %F 6.911 %R 10.1016/j.aca.2024.342910 %X Highly sensitive and rapid detection of ethylene, the smallest alkene of great significance in human physiological metabolism remains a great challenge. In this study, we developed a new photoionization-induced substitution reaction chemical ionization time-of-flight mass spectrometry (PSCI-TOFMS) for trace exhaled ethylene detection. An intriguing ionization phenomenon involving a substitution reaction between the CH2Br2+ reactant ion and ethylene molecule was discovered and studied for the first time. The formation of readily identifiable [CH2Br·C2H4]+ product ion greatly enhanced the ionization efficiency of ethylene, which led to approximately 800-fold improvement of signal intensity over that in single photon ionization mode. The CH2Br2+ reactant ion intensity and ion-molecule reaction time were optimized, and a Nafion tube was employed to eliminate the influence of humidity on the ionization of ethylene. Consequently, a limit of detection (LOD) as low as 0.1 ppbv for ethylene was attained within 30 s at 100 % relative humidity. The application of PSCI-TOFMS on the rapid detection of trace amounts of exhaled ethylene from healthy smoker and non-smoker volunteers demonstrated the satisfactory performance and potential of this system for trace ethylene measurement in clinical diagnosis, atmospheric measurement, and process monitoring.